JP5103184B2 - Gas barrier laminated film - Google Patents

Description

  The present invention relates to a laminated film having excellent gas barrier properties.

Conventionally, a gas barrier plastic film in which a plastic film is used as a base material and an inorganic thin film is formed on the surface thereof is used for packaging articles that require blocking of various gases such as water vapor and oxygen, such as food, industrial products, and pharmaceuticals. Widely used in packaging to prevent deterioration of In addition to packaging applications, the gas barrier plastic film has recently attracted attention as a new application as a transparent conductive sheet used in liquid crystal display elements, solar cells, electromagnetic wave shields, touch panels, EL substrates, color filters, and the like. ing.
With regard to the gas barrier plastic film formed with such an inorganic thin film, several improvements have been studied for various purposes. For example, from the viewpoint of transparency and gas barrier property, a metal oxide is applied to the plastic film. The total light transmittance obtained by sequentially laminating the physical layer / resin / metal oxide layer is 85% or more, and both the oxygen transmission rate and the water vapor transmission rate decrease after immersion for 1 minute in ethyl acetate are 20% or less and A gas barrier film (see Patent Document 1) in which both the oxygen permeability and the water vapor permeability are 1 or less is used to prevent or suppress damage to the metal oxide. It is a barrier film in which organic layers are sequentially laminated alternately, and the difference in solubility factor between the organic layer adjacent to the metal oxide layer and the transparent plastic film is 1.0. Barrier film is above (see Patent Document 2) are disclosed.

  However, in these films, although the intended properties of each are improved to some extent, for example, the gas barrier properties and the adhesion strength between the constituent layers of the laminated film are still insufficient, and the improvement has been desired. .

JP 2003-71968 A JP 2003-231202 A

  The problem to be solved by the present invention is to provide a laminated film having an excellent adhesion strength between constituent layers while exhibiting a high gas barrier property immediately after production and maintaining an excellent gas barrier property.

The present invention
(1) A structural unit layer comprising an anchor coat layer having a thickness of 0.1 to 10 nm and an inorganic thin film formed on the anchor coat layer on an inorganic thin film formed on at least one surface of the base film. A gas barrier laminate film having at least one, and (2) (A) a step of forming an inorganic thin film by vapor deposition on at least one surface of the base film, and (B) a thickness of 0 on the inorganic thin film. The present invention relates to a method for producing a gas barrier laminate film comprising: forming an anchor coat layer having a thickness of 1 to 10 nm, and performing at least one step of forming an inorganic thin film on the anchor coat layer by vapor deposition.

  The present invention provides a laminated film having high gas barrier properties immediately after production and having excellent adhesion strength between the constituent layers of the laminated film while maintaining excellent gas barrier properties.

Hereinafter, the present invention will be described in detail.
The base film of the gas barrier laminate film of the present invention is preferably a thermoplastic polymer film, and the raw material thereof can be used without particular limitation as long as it is a resin that can be used for ordinary packaging materials. Specifically, polyolefins such as homopolymers or copolymers such as ethylene, propylene and butene, amorphous polyolefins such as cyclic polyolefin, polyesters such as polyethylene terephthalate and polyethylene-2,6-naphthalate, nylon 6, nylon 66, nylon 12, polyamide such as copolymer nylon, polyvinyl alcohol, ethylene-vinyl acetate copolymer partial hydrolyzate (EVOH), polyimide, polyetherimide, polysulfone, polyethersulfone, polyetheretherketone, polycarbonate, Examples include polyvinyl butyral, polyarylate, fluororesin, acrylate resin, and biodegradable resin. Among these, polyester, polyamide, polyolefin, and biodegradable resin are preferable from the viewpoint of film strength and cost.
The base film is a known additive such as an antistatic agent, a light blocking agent, an ultraviolet absorber, a plasticizer, a lubricant, a filler, a colorant, a stabilizer, a lubricant, a crosslinking agent, an antiblocking agent, An antioxidant etc. can be contained.

The thermoplastic polymer film as the substrate film is formed by using the above raw materials, but when used as a substrate, it may be unstretched or stretched. Good. Moreover, you may laminate | stack with the other plastic base material. Such a base film can be produced by a conventionally known method. For example, a raw material resin is melted by an extruder, extruded by an annular die or a T die, and rapidly cooled to be oriented substantially amorphously. No unstretched film can be produced. The unstretched film is subjected to a known method such as uniaxial stretching, tenter sequential biaxial stretching, tenter simultaneous biaxial stretching, tubular simultaneous biaxial stretching, or the like. A film stretched in at least a uniaxial direction can be produced by stretching in a direction (horizontal axis) perpendicular thereto.
The thickness of the base film is usually 5 to 500 μm, preferably 10 to 200 μm, depending on its use from the viewpoint of mechanical strength, flexibility, transparency, etc. as the base material of the gas barrier laminate film of the present invention. A sheet-like material selected in a range and having a large thickness is also included. Moreover, there is no restriction | limiting in particular about the width | variety and length of a film, According to a use, it can select suitably.

As an inorganic substance constituting the inorganic thin film formed on at least one surface of the base film, silicon, aluminum, magnesium, zinc, tin, nickel, titanium, hydrocarbon, etc., or their oxides, carbides, nitrides or A mixture thereof may be mentioned, but silicon oxide, aluminum oxide, and hydrocarbon (for example, a substance mainly composed of hydrocarbon such as diamond-like carbon) are preferable. In particular, silicon oxide and aluminum oxide are preferable in that high gas barrier properties can be stably maintained. Although the said inorganic substance may be used individually by 1 type, you may use it in combination of 2 or more type.
As a method for forming the inorganic thin film, any method such as a vapor deposition method and a coating method can be used, but the vapor deposition method is preferable in that a uniform thin film having a high gas barrier property can be obtained. This vapor deposition method includes all methods such as PVD (physical vapor deposition) and CVD (chemical vapor deposition) such as vacuum deposition, ion plating, and sputtering.
The thickness of the inorganic thin film is generally 0.1 to 500 nm, but preferably 0.5 to 40 nm. If it is in the said range, sufficient gas-barrier property will be acquired, and it will be excellent also in transparency, without generating a crack and peeling in an inorganic thin film.

The gas barrier laminate film of the present invention has at least one structural unit layer comprising an anchor coat layer having a thickness of 0.1 to 10 nm and an inorganic thin film formed on the anchor coat layer on the inorganic thin film.
As the anchor coat layer constituting the structural unit layer, a layer made of at least one selected from resins such as thermosetting resins and thermoplastic resins, metals, metal oxides, and metal nitrides can be used.
As a resin such as a thermosetting resin or a thermoplastic resin that forms the anchor coat layer, both solvent-based and water-based resins can be used. Specifically, polyester-based resins, urethane-based resins, acrylic-based resins can be used. Resin, nitrocellulose resin, silicon resin, vinyl alcohol resin, polyvinyl alcohol resin, ethylene vinyl alcohol resin, vinyl modified resin, isocyanate group-containing resin, carbodiimide resin, alkoxyl group-containing resin, epoxy resin, Oxazoline group-containing resins, modified styrene resins, modified silicon resins, alkyl titanates and the like can be used alone or in combination of two or more.
In the present invention, from the viewpoint of gas barrier properties, at least selected from the group consisting of polyester resins, urethane resins, acrylic resins, nitrocellulose resins, silicon resins, isocyanate group-containing resins, and copolymers thereof. It is preferable to use one kind of resin. Of these, polyester resins are preferred.

The polyester resin used in the anchor coat layer can be obtained by reacting a polyvalent carboxylic acid component and a polyhydric alcohol component. Examples of the polyvalent carboxylic acid component include terephthalic acid, isophthalic acid, adipic acid, sebacic acid, azelaic acid, orthophthalic acid, diphenylcarboxylic acid, and dimethylphthalic acid. Examples of the polyhydric alcohol component include ethylene glycol, 1, Examples include 2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, diethylene glycol, neopentyl glycol, dipropylene glycol, 1,6-hexanediol, bisphenol A, and the like.
The polymer constituting the resin has a number average molecular weight of 3,000 to 30,000, preferably 4,000 to 28,000, and more preferably 5,000 to 25 in terms of gas barrier properties and adhesion. , 000.

It is preferable to add a silane coupling agent to the anchor coat layer from the viewpoint of improving the adhesion between the layers. Examples of the silane coupling agent include epoxy group-containing silanes such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxylane, and γ-glycidoxypropyltrimethoxysilane. Coupling agent, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyljetoxylan, N-β (aminoethyl) γ-aminopropyltrimethoxylane, N-β (aminoethyl) γ -Amino group-containing silane coupling agents such as aminopropyltriethoxylane, and mixtures thereof. From the viewpoint of adhesion between layers, preferable silane coupling agents include γ-glycidoxypropyltrimethoxysilane and γ-aminopropyltrimethoxysilane. These silane coupling agents may be used alone or in combination of two or more.
The silane coupling agent is preferably contained in a proportion of 0.1 to 80% by mass, more preferably 1 to 50% by mass with respect to the resin forming the anchor coat layer from the viewpoint of adhesion.

  The anchor coat layer preferably contains a curing agent, and it is preferable to use polyisocyanate as the curing agent. Specific examples include aliphatic polyisocyanates such as hexamethylene diisocyanate and dicyclohexylmethane diisocyanate, and aromatic polyisocyanates such as xylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene diisocyanate, tolidine diisocyanate, and naphthalene diisocyanate. It is done. In particular, bifunctional or higher polyisocyanates are preferable from the viewpoint of improving barrier properties.

  Various known additives can be blended in the anchor coat layer. Examples of such additives include polyhydric alcohols such as glycerin, ethylene glycol, polyethylene glycol and polypropylene glycol, aqueous epoxy resins, lower alcohols such as methanol, ethanol, normal propanol and isopropanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether. , Ethers such as propylene glycol diethyl ether, diethylene glycol monoethyl ether, propylene glycol monoethyl ether, esters such as propylene glycol monoacetate and ethylene glycol monoacetate, antioxidants, weathering stabilizers, UV absorbers, antistatic agents , Pigments, dyes, antibacterial agents, lubricants, inorganic fillers, antiblocking agents, adhesives and the like.

  Moreover, as a metal which forms an anchor coat layer, chromium, aluminum, silicon, nickel, titanium, tin, iron, molybdenum etc. or these 2 or more types of alloys are mentioned preferably from the point of gas barrier property and adhesiveness. Moreover, as a metal oxide or metal nitride, the said metal oxide and nitride are mentioned preferably from the point of gas-barrier property and adhesiveness. In the present invention, the anchor coat layer is more preferably composed of at least one selected from chromium, silicon nitride and titanium oxide from the above viewpoint.

  In the structural unit layer, the upper limit of the thickness of the anchor coat layer is 10 nm, preferably 8 nm, and more preferably 5 nm. Moreover, the lower limit is 0.1 nm, and preferably 0.5 nm. If the thickness is within the above range, good adhesion and the like are preferable. From the above viewpoint, the anchor coat layer has a thickness of 0.1 to 10 nm, preferably 0.1 to 8 nm, more preferably 0.1 to 5 nm from the viewpoint of adhesion and the like. When the anchor coat layer is made of a resin such as the thermosetting resin or thermoplastic resin, the thickness of the anchor coat layer is 0.5 to 10 nm. 8 nm is preferable, and 0.5 to 5 nm is more preferable. This anchor coat layer can be subjected to a crosslinking treatment by electron beam irradiation in order to enhance water resistance and durability.

As a method of forming an anchor coat layer made of a resin such as the thermosetting resin or thermoplastic resin, a known coating method is appropriately adopted. For example, any method such as a reverse roll coater, a gravure coater, a rod coater, an air doctor coater, a spray or a coating method using a brush can be used. Alternatively, the vapor deposition film may be immersed in a resin solution. After application, the solvent can be evaporated using a known drying method such as hot drying such as hot air drying or hot roll drying at a temperature of about 80 to 200 ° C., or infrared drying. Thereby, a laminated film having a uniform coating layer is obtained.
In addition, as a method for forming an anchor coat layer made of at least one selected from metals, metal oxides, and metal nitrides, any method such as vapor deposition and coating can be used. The vapor deposition method is preferable in that it is obtained. For this vapor deposition method, any of the same methods that can be used to form the inorganic thin film can be used.

In the structural unit layer, an inorganic thin film is formed on the anchor coat layer, and the same inorganic thin film formed on the substrate film can be used as the inorganic thin film. The gas barrier laminate film of the present invention has at least one layer of the structural unit layer composed of the anchor coat layer and the inorganic thin film on the inorganic thin film provided on the substrate, but is preferable from the viewpoint of productivity. Preferably have 1 to 3 structural unit layers on the inorganic thin film, more preferably 1 layer or 2 layers. Here, when referring to the number of constituent unit layers, a unit composed of one anchor coat layer and one inorganic thin film is referred to as one constituent unit layer.
From the same point of view, it is preferable that two or more structural unit layers are sequentially provided in the lamination of the structural unit layers, and the anchor coat layer of another structural unit layer is formed on the surface of the inorganic thin film layer of one structural unit layer. It is more preferable to carry out lamination. In the present invention, it is optional to have another layer between the constituent unit layers.

In the present invention, in order to improve the adhesion between the base film and the inorganic thin film, it is preferable to provide an anchor coat layer by applying an anchor coating agent between the base film and the inorganic thin film. As an anchor coat agent, the same thing as what was used for the anchor coat layer which comprises the said structural unit layer can be used.
The thickness of the anchor coat layer provided on the base film is usually 0.1 to 5000 nm, preferably 1 to 2000 nm, more preferably 1 to 1000 nm. If it is in the above range, the slipperiness is good, there is almost no peeling from the base film due to the internal stress of the anchor coat layer itself, and a uniform thickness can be maintained. Is also excellent.
Moreover, in order to improve the applicability | paintability of an anchor coating agent to a base film, and adhesiveness, you may perform surface treatments, such as a normal chemical treatment and electrical discharge treatment, to a base film before application | coating of an anchor coating agent.

  In addition, the gas barrier laminate film of the present invention preferably has a protective layer as the uppermost layer on the side having the structural unit layer. As the resin for forming the protective layer, both solvent-based and water-based resins can be used. Specifically, polyester resins, urethane resins, acrylic resins, polyvinyl alcohol resins, ethylene Unsaturated carboxylic acid copolymer resin, ethylene vinyl alcohol resin, vinyl modified resin, nitrocellulose resin, silicon resin, isocyanate resin, epoxy resin, oxazoline group-containing resin, modified styrene resin, modified silicon resin, Alkyl titanates can be used alone or in combination of two or more. As the protective layer, one or more kinds of inorganic particles selected from silica sol, alumina sol, particulate inorganic filler, and layered inorganic filler are mixed with the one or more kinds of resins in order to improve barrier properties, wearability, and slipperiness. It is preferable to use a layer made of an inorganic particle-containing resin formed by polymerizing the resin raw material in the presence of the inorganic particles.

As the resin for forming the protective layer, the above aqueous resin is preferable from the viewpoint of improving the gas barrier property of the inorganic thin film. Further, the aqueous resin is preferably a polyvinyl alcohol resin, an ethylene vinyl alcohol resin, or an ethylene / unsaturated carboxylic acid copolymer resin.
Below, the said resin layer is demonstrated.

Polyvinyl alcohol can be obtained by a known method, and can usually be obtained by saponifying a polymer of vinyl acetate. A saponification degree of 80% or more can be used, preferably 90% or more, more preferably 95% or more, and particularly preferably 98% or more from the viewpoint of gas barrier properties.
The average degree of polymerization is usually 500 to 3000, and preferably 500 to 2000 in terms of gas barrier properties and stretchability. Moreover, what copolymerized ethylene in the ratio of 40% or less as polyvinyl alcohol can also be used. The aqueous liquid of polyvinyl alcohol is prepared by, for example, supplying a polyvinyl alcohol resin while stirring in normal temperature water, raising the temperature, and stirring at 80 to 95 ° C. for 30 to 60 minutes.

  Ethylene / unsaturated carboxylic acid copolymer is a combination of ethylene and acrylic acid, methacrylic acid, ethacrylic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, monoethyl maleate, maleic anhydride, itaconic anhydride, etc. It is a copolymer with a saturated carboxylic acid, and among them, a copolymer of ethylene and acrylic acid or methacrylic acid is preferable from the viewpoint of versatility. The ethylene-unsaturated carboxylic acid copolymer may contain any other monomer.

  The ethylene component in the ethylene / unsaturated carboxylic acid copolymer is preferably 65 to 90% by mass, more preferably 70 to 85% by mass from the viewpoint of versatility and flexibility, and the unsaturated carboxylic acid component is preferably 10%. It is -35 mass%, More preferably, it is 15-30 mass%. The melt flow rate (MFR) at 190 ° C. under a load of 2160 g of the ethylene / unsaturated carboxylic acid copolymer is preferably 30 to 2000 g / 10 minutes, more preferably 60 to 1500 g, from the viewpoint of the bending resistance of the film. / 10 minutes. The number average molecular weight is preferably in the range of 2000 to 250,000.

In the present invention, from the viewpoint of gas barrier properties, interlayer adhesion, etc., the ethylene / unsaturated carboxylic acid copolymer preferably contains a partially neutralized product, and the degree of neutralization of the partially neutralized product is a gas barrier. From the viewpoint of property, it is preferably 20 to 100%, more preferably 40 to 100%, and particularly preferably 60 to 100%. The degree of neutralization can be obtained from the following formula.
Degree of neutralization = (A / B) x 100 (%)
A: Number of moles of neutralized carboxyl group in 1 g of partially neutralized ethylene / unsaturated carboxylic acid copolymer B: Carboxyl group in 1 g of ethylene / unsaturated carboxylic acid copolymer before partial neutralization In the case of an aqueous liquid, for convenience, the above-mentioned A is defined as (number of metal ions in the solvent) x (valence of the metal ions) and B is partially neutralized with ethylene / unsaturated carboxylic acid. It can be calculated as the number of carboxyl groups in the acid copolymer.

From the viewpoint of gas barrier properties, the ethylene / unsaturated carboxylic acid copolymer may be used as an aqueous liquid comprising the copolymer and an aqueous medium containing ammonia, sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. Preferably, the aqueous medium is used so that the degree of neutralization is 20 to 100%, more preferably 40 to 100%, based on the total number of moles of carboxyl groups of the ethylene / unsaturated carboxylic acid copolymer. Those are preferably used.
In the present invention, the protective layer may be composed of one kind of the resin, but may be used in combination of two or more kinds.

In addition, inorganic particles can be added to the protective layer in order to improve barrier properties and adhesion.
There is no restriction | limiting in particular in the inorganic particle used for this invention, For example, all well-known things, such as an inorganic filler, an inorganic layered compound, a metal oxide sol, can be used.
Examples of inorganic fillers include oxides such as silicon, aluminum, magnesium, calcium, potassium, sodium, titanium, zinc, iron, hydroxides, hydrates, carbonates, and mixtures and composites thereof. .
Examples of the inorganic layered compound include clay minerals typified by kaolinite group, smectite group, mica group and the like, and montmorillonite, hectorite, saponite and the like can be used.
Examples of the metal oxide sol include metal oxides such as silicon, antimony, zirconium, aluminum, cerium, and titanium, or a mixture thereof. Among these, from the viewpoint of hot water resistance and gas barrier properties, those having a reactive functional group capable of being hydrolytically condensed, such as a hydroxy group and an alkoxy group, are preferred, and in the reactive functional group, 10 to 100 mol% of a silanol group, Furthermore, what contains 20-100 mol% is used preferably.

In the present invention, silica particles are preferably used as the inorganic particles from the viewpoint of versatility and stability. Although the said inorganic particle may be used by 1 type, it can also be used in combination of 2 or more type.
The average particle diameter of the inorganic particles is preferably 0.5 nm, more preferably 1 nm, and the upper limit is preferably 2 μm, in view of hot water resistance and cohesive fracture resistance. Preferably it is 200 nm, More preferably, it is 100 nm, More preferably, it is 25 nm, More preferably, it is 10 nm, More preferably, it is 5 nm. Specifically, the average particle diameter is preferably 0.5 to 2 μm, more preferably 0.5 to 200 nm, more preferably 0.5 to 100 nm, more preferably 0.5 to 25 nm, and more. Preferably it is 1-20 nm, More preferably, it is 1-10 nm, More preferably, it is 1-5 nm.

  The thickness of the protective layer is preferably 0.05 to 10 μm, more preferably 0.1 to 3 μm, from the viewpoints of printability and processability. A known coating method is appropriately adopted as the formation method. For example, any method such as a reverse roll coater, a gravure coater, a rod coater, an air doctor coater, a spray or a coating method using a brush can be used. Moreover, you may immerse a vapor deposition film in the resin liquid for protective layers. After coating, moisture can be evaporated using a known drying method such as hot drying such as hot air drying or hot roll drying at a temperature of about 80 to 200 ° C. or infrared drying. Thereby, a laminated film having a uniform coating layer is obtained.

As the gas barrier laminate film of the present invention, the following embodiments can be preferably used from the viewpoint of gas barrier properties and adhesion.
(1) Base film / AC / inorganic thin film / AC / inorganic thin film (2) Base film / AC / inorganic thin film / AC / inorganic thin film / AC / inorganic thin film (3) Base film / AC / inorganic thin film / AC / Inorganic thin film / AC / Inorganic thin film / AC / Inorganic thin film (4) Base film / AC / Inorganic thin film / AC / Inorganic thin film / Protective layer (5) Base film / AC / Inorganic thin film / AC / Inorganic thin film / AC / Inorganic thin film / Protective layer (6) Base film / AC / Inorganic thin film / AC / Inorganic thin film / AC / Inorganic thin film / AC / Inorganic thin film / Protective layer (7) Base film / Inorganic thin film / AC / Inorganic thin film ( 8) Base film / Inorganic thin film / AC / Inorganic thin film / AC / Inorganic thin film (9) Base film / Inorganic thin film / AC / Inorganic thin film / AC / Inorganic thin film / AC / Inorganic thin film (10) Base film / Inorganic Thin film / AC / Inorganic thin film / Protective layer (11) Base material Film / inorganic thin film / AC / inorganic thin film / AC / inorganic thin film / protective layer (12) substrate film / inorganic thin film / AC / inorganic thin film / AC / inorganic thin film / AC / inorganic thin film / protective layer (in the above embodiment) AC refers to the anchor coat layer.)

In the present invention, various gas barrier laminate films in which additional constituent layers are further laminated on the above constituent layers as necessary can be used according to applications.
As a normal embodiment, a gas barrier laminate film in which a plastic film is provided on the inorganic thin film or the protective layer is used for various applications. The thickness of the plastic film is usually 5 to 500 μm, preferably 10 to 200 μm, depending on the application, from the viewpoints of mechanical strength, flexibility, transparency as a substrate of the laminated structure. . Further, the width and length of the film are not particularly limited and can be appropriately selected according to the intended use. For example, by using a resin capable of heat sealing on the surface of the inorganic thin film or the protective layer, heat sealing becomes possible and it can be used as various containers. Examples of the resin that can be heat sealed include known resins such as polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer, ionomer resin, acrylic resin, and biodegradable resin.

  Another embodiment of the gas barrier laminate film is one in which a printing layer is formed on the coating surface of the inorganic thin film or the protective layer, and a heat seal layer is further laminated thereon. As the printing ink for forming the printing layer, aqueous and solvent-based resin-containing printing inks can be used. Here, examples of the resin used in the printing ink include acrylic resins, urethane resins, polyester resins, vinyl chloride resins, vinyl acetate copolymer resins, and mixtures thereof. Furthermore, for printing inks, antistatic agents, light shielding agents, ultraviolet absorbers, plasticizers, lubricants, fillers, colorants, stabilizers, lubricants, antifoaming agents, crosslinking agents, antiblocking agents, antioxidants, etc. These known additives may be added.

Although it does not specifically limit as a printing method for providing a printing layer, Well-known printing methods, such as an offset printing method, a gravure printing method, and a screen printing method, can be used. For drying the solvent after printing, a known drying method such as hot air drying, hot roll drying, or infrared drying can be used.
It is also possible to laminate at least one paper or plastic film between the printing layer and the heat seal layer. As a plastic film, the thing similar to the thermoplastic polymer film as a base film used for the gas barrier laminate film of the present invention can be used. Among these, paper, polyester resin, polyamide resin or biodegradable resin is preferable from the viewpoint of obtaining sufficient rigidity and strength of the laminate.

In the present invention, after forming the anchor coat layer constituting the structural unit layer, or after forming the inorganic thin film constituting the structural unit layer, and further forming the protective layer, the gas barrier property, film quality and coating layer are formed. Heat treatment is preferably performed from the viewpoint of stabilization of quality.
The conditions for the heat treatment vary depending on the type and thickness of the elements constituting the gas barrier laminated film, but are not particularly limited as long as the necessary temperature and time can be maintained. For example, a method of storing in an oven or temperature-controlled room set to the required temperature, a method of blowing hot air, a method of heating with an infrared heater, a method of irradiating light with a lamp, or heating directly by contact with a hot roll or hot plate A method of imparting a light, a method of irradiating with a microwave, or the like can be used. Moreover, even if it heat-processes, after cutting a film into the magnitude | size which is easy to handle, it may heat-process with a film roll. Furthermore, as long as the necessary time and temperature can be obtained, a heating device can be incorporated in a part of a film manufacturing apparatus such as a coater or a slitter, and heating can be performed in the manufacturing process.

  The temperature of the heat treatment is not particularly limited as long as it is a temperature below the melting point of the base material, plastic film, etc. to be used, but it is 60 ° C. or higher because the treatment time necessary for the effect of heat treatment can be set appropriately. It is preferable to carry out at 70 ° C. or higher. The upper limit of the heat treatment temperature is usually 200 ° C., preferably 160 ° C., from the viewpoint of preventing deterioration of gas barrier properties due to thermal decomposition of the elements constituting the gas barrier laminate film. The treatment time depends on the heat treatment temperature, and is preferably shorter as the treatment temperature is higher. For example, when the heat treatment temperature is 60 ° C., the treatment time is about 3 days to 6 months, when it is 80 ° C., the treatment time is about 3 hours to 10 days, and when it is 120 ° C., the treatment time is about 1 hour to 1 day. In the case of 150 ° C., the processing time is about 3 to 60 minutes, but these are merely guidelines and can be appropriately adjusted depending on the type and thickness of the elements constituting the gas barrier laminate film.

The method for producing a gas barrier laminate film of the present invention comprises (A) a step of forming an inorganic thin film by vapor deposition on at least one surface of a base film, and B) a thickness of 0.1 on the inorganic thin film. A step of forming at least one structural unit layer formed by sequentially forming a 10 nm anchor coat layer and an inorganic thin film formed by vapor deposition.
(A) As described above, a uniform thin film having a high gas barrier property can be obtained by the step of forming an inorganic thin film on at least one surface of the base film by vapor deposition. The base film, the inorganic thin film, and the vapor deposition method are as described above.
B) An inorganic thin film is formed by forming an anchor coat layer having a thickness of 0.1 to 10 nm on the inorganic thin film on the surface of the inorganic thin film, and forming the inorganic thin film on the anchor coat layer by vapor deposition. In this multilayer deposition, the adhesion of each layer can be improved, and the gas barrier property can be improved by repeating this one or more times, preferably 1-3 times. The anchor coat layer and the inorganic thin film constituting the structural unit layer in such a method are as described above, and excellent adhesion is obtained by forming the anchor coat layer with a thickness of 0.1 to 10 nm. Can do.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to the following examples. In addition, the evaluation method of the film in the following examples is as follows.
<Water vapor transmission rate>
According to the conditions of JIS Z0222 “moisture-proof packaging container moisture permeability test method” and JIS Z0208 “moisture-proof packaging material moisture permeability test method (cup method)”, the following methods were used for evaluation.
Using two gas barrier laminated films each having a moisture permeable area of 10.0 cm × 10.0 cm square, a bag having about 20 g of anhydrous calcium chloride as a hygroscopic agent and sealed on all sides was produced, and the bag was heated to a temperature of 40 ° C. and a relative humidity of 90 As a guideline, the weight increase was almost constant at intervals of 48 hours or longer, and mass measurement (0.1 mg unit) was performed up to 14 days, and the water vapor transmission rate was calculated from the following formula. In addition, in Table 1-1 and Table 1-2, the value of the water-vapor-permeation rate in the 3rd day is shown.
Water vapor transmission rate (g / m ² / 24h) = (m / s) / t
m: Mass increase in the last two weighing intervals (g)
s; Moisture permeable area (m ² )
t: Time of last two weighing intervals (h) / 24 (h)

<Interlayer adhesion>
In accordance with JIS Z1707, the laminated film is cut into strips with a width of 15 mm, the edges are partially peeled off, and T-type peeling is performed at a rate of 300 mm / min using a peeling tester, and the laminate strength (g / 15 mm) is measured. did.

Example 1
Polyethylene terephthalate resin (hereinafter abbreviated as “PET”; “Novapex” manufactured by Mitsubishi Chemical Corporation) is melt-extruded to form a sheet, stretched in the longitudinal direction at a stretching temperature of 95 ° C. and a stretching ratio of 3.3, and then stretched. A biaxially stretched PET film having a thickness of 12 μm was obtained by stretching in the transverse direction at 110 ° C. and a stretch ratio of 3.3. On one surface of the film, a mixture containing an isocyanate compound (“Coronate L” manufactured by Nippon Polyurethane Industry) and saturated polyester (“Byron 300” manufactured by Toyobo Co., Ltd., number average molecular weight 23000) in a 1: 1 mass ratio was applied and dried. Thus, an anchor coat layer having a thickness of 100 nm was formed.
Next, SiO was evaporated by a high-frequency heating method under a vacuum of 1 × 10 ⁻⁵ Torr using a vacuum deposition apparatus, and an inorganic thin film having a thickness of about 20 nm was formed on the anchor coat layer.
Mixture application drying which blended isocyanate compound ("Coronate L" by Nippon Polyurethane Industry) and saturated polyester ("Byron 300" by Toyobo Co., Ltd.) by 1: 1 mass ratio on the inorganic thin film surface of the obtained inorganic thin film. Thus, an anchor coat layer having a thickness of 0.5 nm was formed.

Next, SiO was evaporated by a high-frequency heating method under a vacuum of 1 × 10 ⁻⁵ Torr using a vacuum deposition apparatus, and an inorganic thin film having a thickness of about 20 nm was formed on the anchor coat layer.
Further, a urethane adhesive (“AD900” and “CAT-RT85” manufactured by Toyo Morton Co., Ltd. in a ratio of 10: 1.5) was applied to the inorganic thin film surface side of the obtained film, dried, and thickened. An adhesive resin layer having a thickness of about 3 μm was formed, and an unstretched polypropylene film having a thickness of 60 μm (“Pyrene Film-CTP 1146” manufactured by Toyobo Co., Ltd.) was laminated on the adhesive resin layer to obtain a laminated film. . Said evaluation was performed about the obtained laminated | multilayer film. The results are shown in Table 1-1.

Example 2
A laminated film was produced in the same manner as in Example 1 except that the thickness of the anchor coat layer between the inorganic thin film layers was 10 nm. Said evaluation was performed about the obtained laminated | multilayer film. The results are shown in Table 1-1.

Example 3
In Example 1, the same procedure was performed except that a silane coupling agent (SH6040 manufactured by Toray Dow Corning Silicone Co., Ltd.) having a solid content ratio of 5% by mass was added to the mixture forming the anchor coat layer between the inorganic thin film layers. Thus, a laminated film was produced. Said evaluation was performed about the obtained laminated | multilayer film. The results are shown in Table 1-1.

Example 4
In Example 1, except that an addition of 50% by mass of a silane coupling agent (SH6040 manufactured by Toray Dow Corning Silicone Co., Ltd.) in a solid content ratio was added to the mixture forming the anchor coat layer between the inorganic thin film layers. A laminated film was produced in the same manner. Said evaluation was performed about the obtained laminated | multilayer film. The results are shown in Table 1-1.

Example 5
In Example 1, a laminated film was produced in the same manner except that the anchor coat layer was not provided on the base PET film. Said evaluation was performed about the obtained laminated | multilayer film. The results are shown in Table 1-1.

Example 6
In Example 1, except that the same anchor coat layer and inorganic thin film as those in Example 1 were sequentially formed in the same manner as in Example 1 on the inorganic thin film surface of the upper layer of the laminated film before application of the adhesive resin layer. A laminated film was produced in the same manner. About the obtained laminated | multilayer film, after laminating | stacking an unstretched polypropylene film like Example 1, the said evaluation was performed. The results are shown in Table 1-2.

Example 7
In Example 1, polyvinyl alcohol (PVA, “GOHSENOL N-300, saponification degree of 98% or more) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and silica sol were further formed on the upper inorganic thin film surface of the laminated film before the application of the adhesive resin layer. A solution containing (Snowtex XS manufactured by Nissan Chemical Industries, Ltd., average particle size 4 to 6 nm) at a solid content mass ratio of 1: 1 was applied by a gravure coating method and then dried to provide a thickness of 0.2 μm. A laminated film was produced in the same manner except that the layer was provided.The obtained laminated film was laminated with an unstretched polypropylene film in the same manner as in Example 1. Then, the above evaluation was performed. It is shown in 2.

Example 8
The following PVA aqueous solution, ethylene / unsaturated carboxylic acid copolymer aqueous solution, and aqueous silica sol aqueous solution were mixed at a solid content mass ratio of 80:10:10 to obtain a coating solution for a protective layer. In Example 1, the protective layer coating solution is applied to the upper inorganic thin film surface of the laminated film before application of the adhesive resin layer by a bar coater so as to have a dry thickness of 0.3 μm to form a protective layer. Then, a laminated film was produced in the same manner as in Example 1 except that an unstretched polypropylene film was laminated thereon in the same manner as in Example 1. Said evaluation was performed about the obtained laminated | multilayer film. The results are shown in Table 1-2.

<Preparation of PVA aqueous solution>
A 10% solid content aqueous solution was prepared using polyvinyl alcohol (PVA, “GOHSENOL N-300” manufactured by Nippon Synthetic Chemical Industry Co., Ltd., saponification degree of 98% or more) and ion-exchanged water.
<Preparation of aqueous solution of ethylene / unsaturated carboxylic acid copolymer>
Ethylene / acrylic acid copolymer (EAA) (acrylic acid 20% by weight, MFR: 300 g / 10 min), ammonia and ion-exchanged water are stirred and mixed at 95 ° C. for 2 hours to obtain a neutralization degree of 75% and a solid content of 20%. An aqueous liquid was prepared.

<Preparation of aqueous silica sol>
An aqueous silica sol was prepared according to the description in paragraphs [0012] to [0031] of JP-A-6-16414. That is, sodium water glass JIS3 was dissolved in a sodium nitrate aqueous solution to prepare a sodium silicate aqueous solution, which was passed through a hydrogen-type cation exchange resin column, a hydroxyl-type anion exchange resin column, and a hydrogen-type cation exchange resin column in this order, An aqueous sodium oxide solution was added to obtain an aqueous silicic acid solution. Next, 5% of the aqueous silicic acid solution was distilled under reduced pressure to remove evaporated water, and the remaining aqueous silicic acid solution was gradually and continuously supplied to continuously carry out reduced pressure distillation to produce a colloidal silica sol. Further, the colloidal silica sol is passed through a hydrogen-type cation exchange resin column, a hydroxyl group-type anion exchange resin column, and a hydrogen-type cation exchange resin column in this order, and immediately after that, special grade ammonia water is added, pH 9, average particle diameter 20 nm, various metals An aqueous silica sol having an oxide concentration of less than 500 ppm (reactive functional group: silanol group ratio: 100 mol%) was obtained.

Example 9
In Example 1, as an anchor coat layer between inorganic thin film layers, a mixture in which an isocyanate compound (“Coronate L” manufactured by Nippon Polyurethane Industry) and a urethane resin (“Mittech NY220A” manufactured by Mitsubishi Chemical Corporation) were mixed at a mass ratio of 1: 1. A laminated film was prepared in the same manner except that an anchor coat layer having a thickness of 0.5 nm was formed by coating and drying. Said evaluation was performed about the obtained laminated | multilayer film. The results are shown in Table 1-2.

Example 10
In Example 1, as an anchor coat layer between the inorganic thin film layers, a mixture in which an isocyanate compound (“Coronate L” manufactured by Nippon Polyurethane Industry) and an acrylic resin (“Paralloid B66” manufactured by Rohm and Haas) were mixed at a mass ratio of 1: 1. A laminated film was prepared in the same manner except that an anchor coat layer having a thickness of 0.5 nm was formed by coating and drying. Said evaluation was performed about the obtained laminated | multilayer film. The results are shown in Table 1-2.

Example 11
In Example 1, as an anchor coat layer between inorganic thin film layers, a mixture containing an isocyanate compound (“Coronate L” manufactured by Nippon Polyurethane Industry) and a nitrocellulose resin (“RS1” manufactured by Daicel Chemical Industries) at a mass ratio of 1: 1. A laminated film was prepared in the same manner except that an anchor coat layer having a thickness of 0.5 nm was formed by coating and drying. Said evaluation was performed about the obtained laminated | multilayer film. The results are shown in Table 1-2.

Example 12
In Example 1, as an anchor coat layer between the inorganic thin film layers, a chromium magnet was used as a target in a DC magnetron sputtering apparatus, and the sputtering was performed in an argon atmosphere of 1 × 10 ⁻² Torr to form a chromium film having a thickness of 0.1 nm. A laminated film was produced in the same manner except that the layer was used. Said evaluation was performed about the obtained laminated | multilayer film. The results are shown in Table 1-2.

Example 13
In Example 1, as an anchor coat layer between inorganic thin film layers, silane and ammonia were introduced by a plasma CVD apparatus, and 0.5 nm thick Si ₃ N ₄ formed in an argon atmosphere of 1 × 10 ⁻² Torr was anchored. A laminated film was produced in the same manner except that the coating layer was used. Said evaluation was performed about the obtained laminated | multilayer film. The results are shown in Table 1-2.

Example 14
In Example 1, as an anchor coat layer between inorganic thin film layers, TiO ₂ having a thickness of 0.2 nm was formed by evaporating TiO ₂ by a high-frequency heating method under a vacuum of 1 × 10 ⁻⁵ Torr using a vacuum deposition apparatus. _A laminated film was prepared in the same manner except that ₂ was an anchor coat layer. Said evaluation was performed about the obtained laminated | multilayer film. The results are shown in Table 1-2.

Comparative Example 1
A laminated film was produced in the same manner as in Example 1 except that an inorganic thin film was directly formed without providing an anchor coat layer between inorganic thin film layers. Said evaluation was performed about the obtained laminated | multilayer film. The results are shown in Table 1-2.
Comparative Example 2
A laminated film was produced in the same manner as in Example 1 except that the thickness of the anchor coat layer between the inorganic thin film layers was 200 nm. Said evaluation was performed about the obtained laminated | multilayer film. The results are shown in Table 1-2.

  The gas-barrier laminated film of the present invention is widely used for packaging of articles that need to block various gases such as water vapor and oxygen, for example, packaging for preventing alteration of food, industrial goods, pharmaceuticals, and the like. Moreover, it can use suitably also as a transparent conductive sheet used with a liquid crystal display element, a solar cell, an electromagnetic wave shield, a touch panel, a substrate for EL, a color filter, etc. besides a packaging use.

Claims (10)

On the inorganic thin film (1) formed on at least one surface of the base film, an anchor coat layer (A) having a thickness of 0.1 to 10 nm and an inorganic thin film (A) formed on the anchor coat layer (A) 2) at least one constitutional unit layer, an anchor coat layer (B) between the base film and the inorganic thin film (1), and the inorganic thin films (1) and (2) each Ri is Do of silicon oxide or aluminum oxide,
The anchor coat layer (A) is a layer composed of at least one selected from the group consisting of a thermosetting resin, a thermoplastic resin, a metal, a metal oxide, and a metal nitride, and the metal oxide is chromium, A gas barrier laminate film which is an oxide of nickel, titanium, tin, iron, molybdenum, or an alloy of two or more of these .   The laminated film according to claim 1, comprising 1 to 3 structural unit layers.   The anchor coat layer (A) is made of at least one resin selected from the group consisting of polyester resins, urethane resins, acrylic resins, nitrocellulose resins, silicon resins, and isocyanate resins. Item 3. The laminated film according to Item 1 or 2.   The laminated film according to any one of claims 1 to 3, wherein the anchor coat layer (A) contains a silane coupling agent.   The laminated film according to claim 1 or 2, wherein the anchor coat layer (A) comprises at least one selected from chromium, titanium oxide, and silicon nitride.   The laminated film according to any one of claims 1 to 5, wherein the anchor coat layer (A) has a thickness of 0.1 to 5 nm.   The laminated film according to claim 1, which has a protective layer as an uppermost layer.   The laminated film according to claim 7, wherein the protective layer is made of an aqueous resin.   The laminated film according to claim 8, wherein the protective layer comprises at least one resin selected from polyvinyl alcohol, ethylene vinyl alcohol, and an ethylene / unsaturated carboxylic acid copolymer. (A) A step of providing an anchor coat layer on at least one surface of the base film and forming an inorganic thin film made of silicon oxide or aluminum oxide on the anchor coat layer by a vapor deposition method; and (B) the above inorganic Forming at least one structural unit layer by sequentially forming an anchor coat layer having a thickness of 0.1 to 10 nm and an inorganic thin film made of silicon oxide or aluminum oxide formed by vapor deposition on the thin film; Yes, and
The anchor coat layer having a thickness of 0.1 to 10 nm in (B) is a layer composed of at least one selected from the group consisting of a thermosetting resin, a thermoplastic resin, a metal, a metal oxide, and a metal nitride. A method for producing a gas barrier laminate film , wherein the metal oxide is chromium, nickel, titanium, tin, iron, molybdenum, or an oxide of two or more of these alloys .